腐植酸相分析测试方法

本文介绍了从土壤样品中快速提取腐植酸的方法及测定腐植酸中碳及其相中铀、金等主要相关元素的相分析方法，应用相分析技术寻找隐伏铀矿床取得了较好的地质效果。     

Photochemical Degradation of Hydrophilic Xenobiotics in the UV/H2O2-process. Influence of Humic Matter on the Degradation Rate of 2-Amino-1-naphthalenesulfonate and Ethylenediaminetetraacetate

Photochemical oxidation methods are able to eliminate hydrophilic xenobiotics with a high efficiency. In waters with high DOC values caused by humic substances (HS) which are able to absorb UV light, problems can result. The degradation rates of the micropollutants using irradiation wavelengths in the range between λ = 200 nm to λ = 260 nm are significantly influenced by HS. This is mainly caused by the high absorption of the HS at shorter wavelength. In the presence of HS, the photolytic degradation of EDTA and FeEDTA was slowed down by an inner filter effect. A similar tendency could be seen for the photolytic degradation of 2-amino-1-naphthalenesulfonate where additional effects to the inner filter effect were also operating. In the UV/H₂O₂-process, the decrease of the degradation rate could be assigned to the ability of the HS to scavenge HO radicals.     

Coagulation Efficiency and Residual Aluminum Content of Polyaluminum Silicate Chloride in Water Treatment

A series of polyaluminum silicate chlorides (PASC), which have different OH^—/Al and Al/Si molar ratios, has been prepared by a copolymerization technique and a composite technique, after which the coagulation efficiency and the residual aluminum content of PASC for water treatment were compared with polyaluminum chloride (PAC) by jar test. The experimental results show that PASC has better coagulation efficiency and lower residual aluminum content than PAC, and the PASC prepared by the copolymerization technique gives a better coagulating effect than that prepared by the composite technique. In addition, the OH^—/Al and Al/Si molar ratios have some effect on the coagulation effect and residual aluminum content of PASC in treated water. With increasing OH^—/Al molar ratio and decreasing Al/Si molar ratio, the residual turbidity and residual aluminum content in treated water diminishes. The pH of the water sample also affects the residual aluminum content of the water and there is a lower residual aluminum content in the neutral pH range.     

海洋浮游植物分解和代谢产物中高分子有机物的紫外、红外和1H-核磁共振光谱特征

用GDX 102树脂从海洋浮游植物三角褐指藻(Phaeodactylum tricornutum)的分解产物和代谢产物中分离提取腐植类物质(DHS,EHS)及乙醇可溶物(DES,EES),用¹H-NMR,IR和UV光谱进行结构分析,并同海水中腐植质(HS)和乙醇可溶物(ES)做了比较。结果表明,DHS,EHS和HS都以高支链烷烃、碳水化合物和氨基酸结构为主要组分,另有少量芳烃和杂环化合物。它们的化学结构很相似,说明DHS和EHS是海水腐植质的重要来源。     

Behavior of Aluminum Adsorption in Different Compost‐Derived Humic Acids

Humic acid plays an important role in the distribution of heavy metals in the environment. The aims of this study were conducted to evaluate the spectroscopic characteristics and aluminum (Al) adsorption of humic acids which were extracted from four composts. The functional groups were determined by Fourier transform infrared spectroscopy (FTIR) and solid‐state ¹³C nuclear magnetic resonance spectroscopy (¹³C‐NMR). The results showed that the aromatic groups were all found in the humic acids of the four composts, and the surface of humic acids included carboxylic group, hydroxylic group, and amino group. The experiment of Al adsorption was described by Freundlich equation. It showed that the adsorption of Al by humic acid from compost of cattle manure was higher, but that from the compost of pig manure, lemon manure, tea manure in equal preparation was lower. The adsorptive behavior was different due to the interaction by functional groups ( OH and  COOH) with Al. These results can describe the fate and transportation of Al in the soil of different organic fertilizer.     

Determination of Partition Coefficients for Selected PAHs between Water and Dissolved Organic Matter

The fate and transport of highly hydrophobic chemicals are affected by the partitioning between water and dissolved organic carbon. Large variation in the partition coefficient (K_DOCw) is often found, due to the selection of model organic matter or potential experimental artifacts. To investigate the roles of the type of organic matter on the partitioning of highly hydrophobic compounds, the partition coefficients of eight selected polycyclic aromatic hydrocarbons (PAHs), with 3–6 aromatic rings, were determined using a passive dosing/extraction method between water and model dissolved organic matter (humic acid, fulvic acid, sodium dodecyl sulfate micelle (SDS), and 2‐hydroxypropyl‐β‐cyclodextrin). Although the K_DOCw values for 3–4 ring PAHs in this study were close to those reported in the literature, experimental K_DOCw values between Aldrich humic acid (AHA) and water were higher than values reported in the literature for 5–6 ring PAHs. The K_DOCw values were highest for AHA, followed by SDS and Suwannee river fulvic acid (SFA). The slopes of the linear regression between log K_DOCw and log K_ow were 1.23 (± 0.13), 0.82 (± 0.09), and 0.59 (± 0.13) for AHA, SDS, and SFA, respectively. The differences in the K_DOCw values between AHA and the other organic matter (SDS, SFA, and CD) increased with increasing hydrophobicity of the PAHs, showing that the sorption of highly hydrophobic chemicals to the humic acid fraction may be important in the presence of mixed organic matter.     

Spectroscopic Characterization of Fulvic Acid Fractions of a Contaminated Groundwater

Two fulvic acid (FA) samples taken from a former gas production facility in the Southwest of Germany were characterized using advanced fluorescence techniques. Steady-state fluorescence (fluorescence excitation, synchronous fluorescence) as well as time-resolved fluorescence were applied. Distinct differences between the sample B22 FA taken within the contamination plume and the sample B53 FA taken downstream were found. Comparison with a model compound for metabolites and humic substances revealed that due to the downstream passage the characteristics of the dissolved organic matter became more humic-like. The assignment of single classes of compounds in the sample B22 FA is discussed in terms of their synchronous fluorescence spectra and fluorescence decay time distribution.     

Ageing of Dissolved Halogenated Humic Substances and the Microbiological Influence on this Process

The distribution of halogens in various fractions of humic substances (HS), separated by their molecular weight, was found to be different for the different halogens. This was demonstrated for chlorine, bromine, and iodine in sewage and brown water samples by applying inductively coupled plasma mass spectrometry coupled with size‐exclusion chromatography. Quantification of the different fractions of iodinated humic substances was obtained by quadrupole mass spectrometry in connection with the isotope dilution technique using an ¹²⁹I‐enriched spike solution. Quantitative analysis was not possible for the corresponding chlorine and bromine species because of spectrometric interferences in the quadrupole instrument. The ageing of HS/halogen species was followed with respect to possible transformations of these species in a ground and sewage water sample up to eight weeks. Even if a distinct structural variation of the humic substance was observed with time by measuring the UV absorption, chlorine remained in the same molecular weight fraction and only a small change was found for the HS/bromine species after eight weeks. In contrast to these findings a substantial transformation of HS/iodine compounds took place, which demonstrated that the transfer probability of halogens from one to another HS fraction is increased with decreasing strength of the halogen bond to carbon. By comparing the results of an original sewage water sample with a filtered one and with another one which was enriched by microorganisms cultivated from the same original sample, a strong microbiological influence on the transformation of HS/iodine species was found. A quantitative balance of the corresponding HS/iodine fractions was calculated for an ageing period of eight weeks showing that iodine was preferably transferred to newly formed UV active HS substances of high molecular weight. In total, no iodine was released from the humic substances.     

Combined Effects of Molecular Size and Electroendosmotic Flow on the Capillary Electrophoretic Behaviour of Humic Substances

The electroendosmotic flow (EOF), generated by the migration of solvated ions near the charged capillary surface, is an important factor in determining the capillary electrophoretic behaviour of humic substances (HS). We investigated the electrophoretic mobilities of HS fractions of reduced molecular-weight polydispersity extracted from peat and from a spodosol either in the presence or after suppression of the EOF. When the EOF was not suppressed, HS migrated to the cathode in spite of their negative charge. Fractionation of HS according to molecular size was achieved in polyacrylamide-coated capillaries filled with 0.05 M tris-phosphate buffer. In uncoated capillaries filled with the same buffer, all fractions had very close mobilities. Addition of polyethylene glycol MW 4000 at concentrations above its entanglement threshold caused the migration times of larger molecules to increase more than those of smaller molecules. The separation was a linear function of molecular size up to 75000 g mol^–1 for peat HS and to 50000 g mol^–1 for HS extracted from the spodosol.     

Degradation and Transformation of Aquatic Humic Substances by Laccase-producing Fungi Cladosporium cladosporioides and Polyporus versicolor

A phenoloxidase-producing fungus – Cladosporium cladosporioides – was isolated from water of a bog lake. At high concentrations of carbon (333 mM) and nitrogen (12 mM), the fungus demonstrated the formation of a laccase and a high ligninolytic activity. After addition of riverine or groundwater humic substances into culture media (ca. 1 mg mL^–1), the fungus showed the ability of degrading (utilizing) of about 60% of these substances. However, the exact quantification of the degree of degradation was difficult because of adsorption of humic matter on fungal mycelium. Reisolated humic substances were lower in aromatic and higher in aliphatic structures. A crude enzyme from the C. cladosporioides culture showed only low activity in decolorizing humic substances, whereas decolorization up to 50% was observed when using a laccase preparation from Polyporus versicolor, and especially in the presence of a redox mediator.